(Polyfluoroaryl)fluoroanions of aluminum, gallium, and indium of enhanced utility, uses thereof, and products based thereon

Abstract

The (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium are novel weakly coordinating anions which are are highly fluorinated. (Polyfluoroaryl)fluoroanions of one such type contain at least one ring substituent other than fluorine. These (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium have greater solubility in organic solvents, or have a coordinative ability essentially equal to or less than that of the corresponding (polyfluoroaryl)fluoroanion of aluminum, gallium, or indium in which the substituent is replaced by fluorine. Another type of new (polyfluoroaryl)fluoroanion of aluminum, gallium, and indium have 1-3 perfluorinated fused ring groups and 2-0 perfluorophenyl groups. When used as a cocatalyst in the formation of novel catalytic complexes with d- or f-block metal compounds having at least one leaving group such as a methyl group, these anions, because of their weak coordination to the metal center, do not interefere in the ethylene polymerization process, while affecting the the propylene process favorably, if highly isotactic polypropylene is desired. Thus, the (polyfluoroaryl)fluoroanions of aluminum, gallium, and indium of this invention are useful in various polymerization processes such as are described.

What is claimed is:  
     
       1. A process for polymerizing a polymerizable olefinic monomer or copolymerizing two or more copolymerizable olefinic monomers, which process comprises contacting said monomer or monomers with a polymerization catalyst complex which comprises a cation formed from a d-block or f-block metal compound by abstraction therefrom of a leaving group, and formation of an ion pair comprised of a cation of said d-block or f-block metal compound and a (polyfluoroaryl)fluoroanion of aluminum, gallium, or indium of the formula: 
       
         
           [ER′R″R′″F] ⊖   
         
       
       wherein E is aluminum, gallium, or indium, wherein F is fluorine, wherein R′ is a fluoroaryl group having at least one additional substituent other than fluorine, wherein R″ and R′″ each is, independently, (i) a fluoroaryl group having at least one additional substituent other than fluorine, or (ii) a fluorinated hydrocarbyl group devoid of additional substitution. 
     
     
       2. A process of claim or  1  wherein said monomer or monomers comprise(s) a 1-olefin, a vinylaromatic monomer, or an ester of acrylic or methacrylic acid. 
     
     
       3. A process of claim  1  wherein said metal compound is a metallocene represented by the formula: 
       
         
           Q a Cp b ML c X d    
         
       
       where Cp independently in each occurrence is a cyclopentadienyl-moiety-containing group which has in the range of 5 to about 24 carbon atoms; Q is a bridging group or ansa group that links two Cp groups together; M is a d- or f-block metal atom; each L is, independently, a leaving group that is bonded to the d- or f-block metal atom and is capable of being abstracted by an organocation of the organocation salt of the (polyfluoroaryl)fluoroanion used in forming the catalytic complex; X is a group other than a leaving group that is bonded to the d- or f-block metal atom and does not detrimentally affect propagation of the polymer chain during polymerization; a is 0 or 1; b is a whole integer from 1 to 3; c is 1 to 3; d is 0 or 1; and the sum of c and d is at least 2. 
     
     
       4. A process of claim  3  wherein M is a Group 4 metal atom, wherein a is 0, wherein b is 1, and the sum of c and d is 3. 
     
     
       5. A process of claim  3  wherein M is a Group 4 metal atom, wherein b is 2 and the sum of c and d is 2. 
     
     
       6. A process of claim  1  wherein said metal compound is a metallocene represented by the formula:                    
       wherein M is a metal of Group 3 (other than scandium), Groups 4-10, or the lanthanide series; L is a group containing a cyclic, delocalized, anionic, pi-system through which the group is bound to M, and which group is also bound to Z; Z is a moiety comprising boron, or a member of Group 14 of the Periodic Table, and optionally sulfur or oxygen, this moiety having up to about 20 non-hydrogen atoms; Y is an anionic or nonanionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to about 20 non-hydrogen atoms; R is a leaving group; X is a non-leaving group which does not detrimentally affect propagation of the polymer chain during polymerization, n is 1 to 4, m is 0 to 3, with the sum of n plus m being 1 to 4 depending upon the valence of M. 
     
     
       7. A process of claim  6  wherein M is a titanium, zirconium or hafnium atom, L is a cyclopentadienyl group or a substituted cyclopentadienyl group, Z is a dihydrocarbylsilyl group, Y is a hydrocarbylamido group, R is methyl, n is 2, and m is 0. 
     
     
       8. A process of claim  6  wherein M is a titanium or zirconium atom, L is a tetramethylcyclopentadienyl group, Z is a dimethylsilyl group, Y is a tert-butylamido group, R is methyl, n is 2, and m is 0. 
     
     
       9. A complex which comprises a cation formed from a d-block or f-block metal compound by loss of a leaving group and formation of an ion pair comprised of (a) said cation formed from a d-block or f-block metal compound and (b) a (polyfluoroaryl)fluoroanion of aluminum, gallium, or indium of the formula: 
       
         
           [ER′R″R′″F] ⊖   
         
       
       wherein E is aluminum, gallium, or indium, wherein F is fluorine, wherein R′ is a fluoroaryl group having at least one additional substituent other than fluorine, wherein R″ and R′″ each is, independently, (i) a fluoroaryl group having at least one additional substituent other than fluorine, or (ii) a fluorinated aryl group devoid of additional substitution. 
     
     
       10. A complex of claim  9  wherein the metal of said metal compound is a metal from Groups 4 to 8 of the Periodic Table. 
     
     
       11. A complex of claim  9  wherein the metal of said metal compound is thorium, titanium, zirconium, or hafnium. 
     
     
       12. A complex of claim  9  wherein said (polyfluoroaryl)fluoroanion is a weakly coordinating anion that has a coordinative ability essentially equivalent to or less than that of the corresponding (polyfluoroaryl)fluoroanion in which each substituent other than fluorine is replaced by a fluorine atom, when the coordinative abilities of the (polyfluoroaryl)fluoroanions are compared as salts of [1,2-(9-fluorenyl) 2 C 2 H 4 ZrMe] ⊕ . 
     
     
       13. A complex of claim  9  wherein said (polyfluoroaryl)fluoroanion has a greater solubility in n-hexane at 20° C. than that of the corresponding (polyfluoroaryl)fluoroanion in which each substituent other than fluorine is replaced by a fluorine atom, and in which the counterion for each (polyfluoroaryl)fluoroanion is the same. 
     
     
       14. A complex of claim  9  wherein said (polyfluoroaryl)fluoroanion has the formula:                    
       wherein E is aluminum, gallium, or indium, wherein F is fluorine, and wherein R is a substituent other than a fluorine atom, and x is from 1 to 3. 
     
     
       15. A complex of claim  9  wherein said (polyfluoroaryl)fluoroanion has the formula:                    
       wherein E is aluminum, gallium, or indium, wherein F is fluorine, and wherein each R is, independently, a substituent other than a fluorine atom, and x is from 1 to 3. 
     
     
       16. A complex of claim  9  wherein at least one said additional univalent substituent of said (polyfluoroaryl)fluoroanion is an electron-withdrawing substituent. 
     
     
       17. A complex of claim  9  wherein at least one said additional univalent substituent of said (polyfluoroaryl)fluoroanion is an organic solvent solubility-enhancing substituent as determined in n-hexane at 20° C. 
     
     
       18. A complex of claim  9  wherein said metal compound is a metallocene represented by the formula:                    
       wherein M is a metal of Group 3 (other than scandium), Groups 4-10, or the lanthanide series; L is a group containing a cyclic, delocalized, anionic, pi-system through which the group is bound to M, and which group is also bound to Z; Z is a moiety comprising boron, or a member of Group 14 of the Periodic Table, and optionally sulfur or oxygen, this moiety having up to about 20 non-hydrogen atoms; Y is an anionic or nonanionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to about 20 non-hydrogen atoms; R is a leaving group; X is a non-leaving group which does not detrimentally affect propagation of a polymer chain which is formed during polymerization, n is 1 to 4, m is 0 to 3, with the sum of n plus m being 1 to 4 depending upon the valence of M. 
     
     
       19. A complex of claim  18  wherein M is a titanium, zirconium, or hafnium atom, L is a cyclopentadienyl group or a substituted cyclopentadienyl group, Z is a dihydrocarbylsilyl group, Y is a hydrocarbylamido group, R is methyl, n is 2, and m is 0. 
     
     
       20. A complex of claim  18  wherein M is a titanium or zirconium atom, L is a tetramethylcyclopentadienyl group, Z is a dimethylsilyl group, Y is a tert-butylamido group, R is methyl, n is 2, and m is 0. 
     
     
       21. A complex of claim  9  wherein said metal compound is a metallocene represented by the formula: 
       
         
           Q a Cp b MG c X d    
         
       
       where Cp independently in each occurrence is a cyclopentadienyl-moiety-containing group which has in the range of 5 to about 24 carbon atoms; Q is a bridging group or ansa group that links two Cp groups together; M is a d- or f-block metal atom; each G is, independently, a leaving group that is bonded to the d- or f-block metal atom and is capable of being abstracted by an organocation of the organocation salt of the (polyfluoroaryl)fluoroanion used in forming the catalytic complex; X is a group other than a leaving group that is bonded to the d- or f-block metal atom and does not detrimentally affect propagation of a polymer chain which is formed during polymerization; a is 0 or 1; b is a whole integer from 1 to 3; c is 1 to 3; d is 0 or 1; and the sum of c and d is at least 2. 
     
     
       22. A complex of claim  21  wherein M is a Group 4 metal atom, wherein a is 0, wherein b is 1, and the sum of c and d is 3. 
     
     
       23. A complex of claim  21  wherein M is a Group 4 metal atom, wherein b is 2 and the sum of c and d is 2. 
     
     
       24. A process for preparing a catalytic complex or ion pair, which process comprises contacting a d-block or f-block metal compound having at least one leaving group with a salt of a (polyfluoroaryl)fluoroanion of aluminum, gallium, or indium of the formula: 
       
         
           [ER′R″R′″F] ⊖   
         
       
       wherein E is aluminum, gallium, or indium, wherein F is fluorine, wherein R′ is a fluoroaryl group having at least one additional substituent other than fluorine, R″ and R′″ each is, independently, (i) a fluoroaryl group having at least one additional substituent other than fluorine, or (ii) a fluorinated hydrocarbyl group devoid of additional substitution, in a suitably anhydrous liquid medium and in a suitably inert atmosphere or environment, such that a leaving group is abstracted from the d-block or f-block metal compound and an ion pair is formed, comprised of a cation formed from said d-block or f-block metal compound and said (polyfluoroaryl)fluoroanion. 
     
     
       25. A process of claim  24  wherein said metal compound is a metallocene represented by the formula: 
       
         
           Q a Cp b MG c X d    
         
       
       where Cp independently in each occurrence is a cyclopentadienyl-moiety-containing group which has in the range of 5 to about 24 carbon atoms; Q is a bridging group or ansa group that links two Cp groups together; M is a d- or f-block metal atom; each G is, independently, a leaving group that is bonded to the d- or f-block metal atom and is capable of being abstracted by an organocation of the organocation salt of the (polyfluoroaryl)fluoroanion used in forming the catalytic complex; X is a group other than a leaving group that is bonded to the d- or f-block metal atom and does not detrimentally affect propagation of a polymer chain which is formed during polymerization; a is 0 or 1; b is a whole integer from 1 to 3; c is 1 to 3; d is 0 or 1; and the sum of c and d is at least 2. 
     
     
       26. A process of claim  25  wherein M is a Group 4 metal atom, wherein a is 0, wherein b is 1, and the sum of c and d is 3. 
     
     
       27. A process of claim  25  wherein M is a Group 4 metal atom, wherein b is 2 and the sum of c and d is 2. 
     
     
       28. A process of claim  26  wherein said metal compound is a metallocene represented by the formula:                    
       wherein M is a metal of Group 3 (other than scandium), Groups 4-10, or the lanthanide series; L is a group containing a cyclic, delocalized, anionic, pi-system through which the group is bound to M, and which group is also bound to Z; Z is a moiety comprising boron, or a member of Group 14 of the Periodic Table, and optionally sulfur or oxygen, this moiety having up to about 20 non-hydrogen atoms; Y is an anionic or nonanionic ligand group bonded to Z and M comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to about 20 non-hydrogen atoms; R is a leaving group; X is a non-leaving group which does not detrimentally affect propagation of a polymer chain which is formed during polymerization, n is 1 to 4, m is 0 to 3, with the sum of n plus m being 1 to 4 depending upon the valence of M. 
     
     
       29. A process of claim  28  wherein M is a titanium, zirconium or hafnium atom, L is a cyclopentadienyl group or a substituted cyclopentadienyl group, Z is a dihydrocarbylsilyl group, Y is a hydrocarbylamido group, R is methyl, n is 2, and m is 0. 
     
     
       30. A process of claim  28  wherein M is a titanium or zirconium atom, L is a tetramethylcyclopentadienyl group, Z is a dimethylsilyl group, Y is a tert-butylamido group, R is methyl, n is 2, and m is 0.